Strength improvement admixture

ABSTRACT

A strength improvement admixture composition is provided that increases the compressive strength of cementitious compositions without negatively increasing the setting time. The admixture comprises the components of a polycarboxylate dispersant, a set retarder, and a strength improvement additive.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. Ser. No. 10/787,507 filed Feb.26, 2004, which claims the benefit of the filing date of United StatesProvisional Application for Patent Ser. No. 60/450,374 filed Feb. 26,2003, both of which are hereby incorporated herein by reference in theirentireties.

BACKGROUND

Dispersants have been used in the construction industry, eithersingularly or as part of water-reducing compositions, to dispersecementitious mixtures allowing for a reduction in mix water contentwhile maintaining flowability and workability of the mixture. Thisreduction in the water cement ratio leads to increases in compressivestrength and is one of the main reasons that water-reducing admixturesare used. Dispersants such as sulfonated melamine formaldehydecondensate (SMF), sulfonated naphthalene formaldehyde condensate (BNS),and lignosulfonates are commonly used as dispersants. However, thesecompounds are best suited for specific tasks. BNS and SMF areparticularly difficult to use reliably and cost effectively at lowlevels and are best suited for use as high-range water reducers (>12%water-reduction). Lignosulfonates in general tend to be best suited forlower water-reduction levels (<15%) and can cause excessive setretardation when used at higher amounts. Other materials such as saltsof hydroxycarboxylic acids and sugars such as glucose or sucrose canalso provide some degree of water reduction. In addition to the waterreduction, the hydroxycarboxylic acids and sugars have commonly beenused to retard the rate of set, which can lead to further improvementsin compressive strength.

Dispersants such as BNS or lignosulfonates are often combined withadditional components like sugars to achieve improved strengthperformance. These compositions usually must also contain acceleratingcomponents to offset excessive retardation. Even in combination withaccelerating type components, formulated water reducers such as thesecan still retard excessively when used across a wide water reductionrange in concrete mixtures containing pozzolans such as fly ash or slag,or in concrete that is mixed and placed at cool temperatures (50° F. orbelow). Additional accelerating admixtures are sometimes needed in aneffort to offset this excessive retardation and depending on theseverity, can be minimally effective. Excessive retardation isundesirable in that it can delay jobsite activity, prevent forms frombeing stripped, delay finishing operations or lead to low early agestrengths. Providing an admixture with full range (Type A to F) waterreducing capability and improved compressive strength while maintainingnormal setting or easily controllable setting characteristics isdesirable.

One improvement in the prior art was to use polycarboxylate dispersants.Polycarboxylate dispersants are structured with a polymeric backbone,such as a carbon chain backbone, with pendant moieties that provide thedispersing capabilities of the molecule. For example, polyacrylic acidhas carboxylic groups attached to the backbone. additionally, side chainmoieties such as polyoxyalkylenes can be attached to the carboxylicgroups to provide further dispersing capabilities. These polymers attachto the cement grains and produce dispersion by means of bothelectrostatic repulsion and steric hindrance, resulting in increasedfluidity.

It is desirable to provide an admixture comprising a polycarboxylatedispersant that improves the compressive strength of cementitiouscompositions without exponentially increasing the set time when usedwith set retarders, as is observed with BNS and lignosulfonatedispersants. Therefore, an admixture which improves the compressivestrength of the hardened cementitious composition without producing anyother changes would be advantageous in the industry.

U.S. Pat. No. 4,401,472 to Gerber discloses an additive comprising apoly(hydroxyalkylated)polyethyleneamine or apoly(hydroxyalkylated)polyethyleneimine or mixtures thereof, wherein theadditive is present in a hydraulic cement mix in an amount sufficient toincrease the compressive strength of the hardened mix.

U.S. Pat. No. 4,519,842 to Gerber discloses a cement mix comprising anadmixture of poly(hydroxyalkylated)polyamine, alkoxylatedpoly(hydroxyalkylated)polyamine hydroxyalkylated derivatives of thecompounds hydrazine, 1,2, diaminopropane and polyglycoldiamine andmixtures thereof, wherein the admixture is present in amounts sufficientto increase the compressive strength of the hardened cement mix.

SUMMARY

An admixture composition that improves the compressive strength ofcementitious compositions without negatively effecting the setting timeis provided which comprises the components of polycarboxylatedispersant, set retarder and a strength improvement additive selectedfrom the group consisting of poly(hydroxyalkylated)polyethyleneamines,poly(hydroxyalkylated)polyethylenepolyamines,poly(hydroxyalkylated)polyethyleneimines,poly(hydroxyalkylated)polyamines, hydrazines, 1,2-diaminopropane,polyglycoldiamine, poly(hydroxyalkyl)amines and mixtures thereof.

A cementitious composition is provided that comprises hydraulic cementand a strength improvement admixture composition, wherein the admixturecomposition comprises the components of polycarboxylate dispersant, setretarder and a strength improvement additive selected from the groupconsisting of poly(hydroxyalkylated)polyethyleneamines,poly(hydroxyalkylated)polyethylenepolyamines,poly(hydroxyalkylated)polyethyleneimines,poly(hydroxyalkylated)polyamines, hydrazines, 1,2-diaminopropane,polyglycoldiamine, poly(hydroxyalkyl)amines and mixtures thereof.

A method of making a cementitious composition is provided whichcomprises forming a mixture of water, hydraulic cement and a strengthimprovement admixture composition, wherein the admixture compositioncomprises the components of polycarboxylate dispersant, set retarder anda strength improvement additive selected from the group consisting ofpoly(hydroxyalkylated)polyethyleneamines,poly(hydroxyalkylated)polyethylenepolyamines,poly(hydroxyalkylated)polyethyleneimines,poly(hydroxyalkylated)polyamines, hydrazines, 1,2-diaminopropane,polyglycoldiamine, poly(hydroxyalkyl)amines and mixtures thereof.

DETAILED DESCRIPTION

A strength improvement admixture composition for cementitiouscompositions is provided, as well as a novel cementitious compositioncontaining such an admixture composition and a method for preparing sucha cementitious composition.

It is known in the prior art that when a BNS, SMF or lignin dispersantis combined with a set retarder, exponential retardation, as compared toadditive retardation, is observed. The excessive retardation caused bythe combination serves to greatly increase the setting time of thecementitious composition. It has been demonstrated that when a BNS, SMFor lignin dispersant is added to a cementitious composition containing aset retarder, there is a very narrow range of addition in which toimprove the strength of a cementitious mix before retardation becomesexcessive. In comparison, polycarboxylate dispersants have a wide rangeof addition with little or no retardation effect upon the cementitiousmixture and provide increased compressive strength to cementitiousmixtures.

Polycarboxylate dispersants are very effective at dispersing andreducing the water content in hydraulic cementitious compositions. Thesedispersants operate by binding to a cement particle and developing bothelectrostatic and steric repulsive forces, thereby keeping the particlesapart, resulting in a more fluid system.

The term polycarboxylate dispersant used throughout this specificationrefers to polymers with a carbon backbone with pendant side chains,wherein at least a portion of the side chains are attached to thebackbone through a carboxyl group or an ether group. The term dispersantis also meant to include those chemicals which also function as aplasticizer, water reducer, fluidizer, antiflocculating agent, orsuperplasticizer for cementitious compositions. Examples ofpolycarboxylate dispersants can be found in U.S. Pat. No. 6,267,814,U.S. Pat. No. 6,290,770, U.S. Pat. No. 6,310,143, U.S. Pat. No.6,187,841, U.S. Pat. No. 5,158,996, U.S. Pat. No. 6,008,275, U.S. Pat.No. 6,136,950, U.S. Pat. No. 6,284,867, U.S. Pat. No. 5,609,681, U.S.Pat. No. 5,494,516; U.S. Pat. No. 5,674,929, U.S. Pat. No. 5,660,626,U.S. Pat. No. 5,668,195, U.S. Pat. No. 5,661,206, U.S. Pat. No.5,358,566, U.S. Pat. No. 5,162,402, U.S. Pat. No. 5,798,425, U.S. Pat.No. 5,612,396, U.S. Pat. No. 6,063,184, and U.S. Pat. No. 5,912,284,U.S. Pat. No. 5,840,114, U.S. Pat. No. 5,753,744, U.S. Pat. No.5,728,207, U.S. Pat. No. 5,725,657, U.S. Pat. No. 5,703,174, U.S. Pat.No. 5,665,158, U.S. Pat. No. 5,643,978, U.S. Pat. No. 5,633,298, U.S.Pat. No. 5,583,183, and U.S. Pat. No. 5,393,343, which are allincorporated herein by reference.

In one embodiment the admixture composition comprises about 5% to about80% polycarboxylate dispersant based on the total dry weight of theadmixture composition components. In another embodiment the admixturecomposition comprises about 20% to about 60% polycarboxylate dispersantbased on the total dry weight of the admixture composition components.In another embodiment a cementitious composition comprises about 0.02%to about 2% polycarboxylate dispersant by weight of cementitious binder.In a further embodiment a cementitious composition comprises about 0.02%to about 0.24% polycarboxylate dispersant by weight of cementitiousbinder.

The polycarboxylate dispersants used in the system can be at least oneof the dispersant formulas a) through k):

-   a) a dispersant of Formula (I):

wherein in Formula (I)

-   -   X is at least one of hydrogen, an alkali earth metal ion, an        alkaline earth metal ion, ammonium ion, or amine;    -   R is at least one of C₁ to C₆ alkyl(ene) ether or mixtures        thereof or C₁ to C₆ alkyl(ene)imine or mixtures thereof;    -   Q is at least one of oxygen, NH, or sulfur;    -   p is a number from 1 to about 300 resulting in at least one of a        linear side chain or branched side chain;    -   R₁ is at least one of hydrogen, C₁ to C₂₀ hydrocarbon, or        functionalized hydrocarbon containing at least one of —OH,        —COOH, an ester or amide derivative of —COOH, sulfonic acid, an        ester or amide derivative of sulfonic acid, amine, or epoxy;    -   Y is at least one of hydrogen, an alkali earth metal ion, an        alkaline earth metal ion, ammonium ion, amine, a hydrophobic        hydrocarbon or polyalkylene oxide moiety that functions as a        defoamer;    -   m, m′, m″, n, n′, and n″ are each independently 0 or an integer        between 1 and about 20;    -   Z is a moiety containing at least one of i) at least one amine        and one acid group, ii) two functional groups capable of        incorporating into the backbone selected from the group        consisting of dianhydrides, dialdehydes, and di-acid-chlorides,        or iii) an imide residue; and    -   wherein a, b, c, and d reflect the mole fraction of each unit        wherein the sum of a, b, c, and d equal one, wherein a, b, c,        and d are each a value greater than or equal to zero and less        than one, and at least two of a, b, c, and d are greater than        zero;

-   b) a dispersant of Formula (II):

-   -   wherein in Formula (II):    -   A is COOM or optionally in the “y” structure an acid anhydride        group (—CO—O—CO—) is formed in place of the A groups between the        carbon atoms to which the A groups are bonded to form an        anhydride;    -   B is COOM    -   M is hydrogen, a transition metal cation, the residue of a        hydrophobic polyalkylene glycol or polysiloxane, an alkali metal        ion, an alkaline earth metal ion, ferrous ion, aluminum ion,        (alkanol)ammonium ion, or (alkyl)ammonium ion;    -   R is a C₂₋₆ alkylene radical;    -   R1 is a C₁₋₂₀ alkyl, C₆₋₉ cycloalkyl, or phenyl group;    -   x, y, and z are a number from 0.01 to 100;    -   m is a number from 1 to 100; and    -   n is a number from 10 to 100;

-   c) a dispersant comprising at least one polymer or a salt thereof    having the form of a copolymer of    -   i) a maleic anhydride half-ester with a compound of the formula        RO(AO)_(m)H, wherein R is a C₁-C₂₀ alkyl group, A is a C₂₋₄        alkylene group, and m is an integer from 2-16; and    -   ii) a monomer having the formula CH₂═CHCH₂—(OA)_(n)OR, wherein n        is an integer from 1-90 and R is a C₁₋₂₀ alkyl group;

-   d) a dispersant obtained by copolymerizing 5 to 98% by weight of an    (alkoxy)polyalkylene glycol mono(meth)acrylic ester monomer (a)    represented by the following general formula (1):

-   -   wherein R₁ stands for hydrogen atom or a methyl group, R₂O for        one species or a mixture of two or more species of oxyalkylene        group of 2 to 4 carbon atoms, providing two or more species of        the mixture may be added either in the form of a block or in a        random form, R₃ for a hydrogen atom or an alkyl group of 1 to 5        carbon atoms, and m is a value indicating the average addition        mol number of oxyalkylene groups that is an integer in the range        of 1 to 100, 95 to 2% by weight of a (meth)acrylic acid        monomer (b) represented by the above general formula (2),        wherein R₄ and R₅ are each independently a hydrogen atom or a        methyl group, and M₁ for a hydrogen atom, a monovalent metal        atom, a divalent metal atom, an ammonium group, or an organic        amine group, and 0 to 50% by weight of other monomer (c)        copolymerizable with these monomers, provided that the total        amount of (a), (b), and (c) is 100% by weight;

-   e) a graft polymer that is a polycarboxylic acid or a salt thereof,    having side chains derived from at least one species selected from    the group consisting of oligoalkyleneglycols, polyalcohols,    polyoxyalkylene amines, and polyalkylene glycols;

-   f) a dispersant of Formula (III):

-   wherein in Formula (III):-   D=a component selected from the group consisting of the structure    d1, the structure d2, and mixtures thereof;-   X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-Methyl Phenyl, or Sulfonated    Phenyl;-   Y=H or —COOM;-   R=H or CH₃;-   Z=H, —SO₃M, —PO₃M, —COOM, —O(CH₂)_(n)OR₃ where n=2 to 6, —COOR₃, or    —(CH₂)_(n)OR₃ where n=0 to 6, —CONHR₃, —CONHC(CH₃)₂CH₂SO₃M,    —COO(CHR₄)_(n)OH where n=2 to 6, or —O(CH₂)_(n)OR₄ wherein n=2 to 6;-   R₁, R₂, R₃, R₅ are each independently —(CHRCH₂O)_(m)R₄ random    copolymer of oxyethylene units and oxypropylene units where m=10 to    500 and wherein the amount of oxyethylene in the random copolymer is    from about 60% to 100% and the amount of oxypropylene in the random    copolymer is from 0% to about 40%;-   R₄=H, Methyl, C₂ to about C₆ Alkyl, or about C₆ to about C₁₀ aryl;-   M=H, Alkali Metal, Alkaline Earth Metal, Ammonium, Amine, triethanol    amine, Methyl, or C₂ to about C₆ Alkyl;-   a=0 to about 0.8;-   b=about 0.2 to about 1.0;-   c=0 to about 0.5;-   d=0 to about 0.5; and-   wherein a, b, c, and d represent the mole fraction of each unit and    the sum of a, b, c, and d is 1.0;-   g) a dispersant of Formula (IV):

-   -   wherein in Formula (IV):    -   the “b” structure is one of a carboxylic acid monomer, an        ethylenically unsaturated monomer, or maleic anhydride wherein        an acid anhydride group (—CO—O—CO—) is formed in place of the        groups Y and Z between the carbon atoms to which the groups Y        and Z are bonded respectively, and the “b” structure must        include at least one moiety with a pendant ester linkage and at        least one moiety with a pendant amide linkage;

-   X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-Methyl Phenyl, p-Ethyl Phenyl,    Carboxylated Phenyl, or Sulfonated Phenyl;

-   Y=H, —COOM, —COOH, or W;

-   W=a hydrophobic defoamer represented by the formula    R₅O—(CH₂CH₂O)_(s)—(CH₂C(CH₃)HO)_(t)—(CH₂CH₂O)_(u) where s, t, and u    are integers from 0 to 200 with the proviso that t>(s+u) and wherein    the total amount of hydrophobic defoamer is present in an amount    less than about 10% by weight of the polycarboxylate dispersant;

-   Z=H, —COOM, —O(CH₂)_(n)OR₃ where n=2 to 6, —COOR₃, —(CH₂)_(n)OR₃    where n=0 to 6, or —CONHR₃;

-   R₁=H, or CH₃;

-   R₂, R₃, are each independently a random copolymer of oxyethylene    units and oxypropylene units of the general formula    —(CH(R₁)CH₂O)_(m)R₄ where m=10 to 500 and wherein the amount of    oxyethylene in the random copolymer is from about 60% to 100% and    the amount of oxypropylene in the random copolymer is from 0% to    about 40%;

-   R₄=H, Methyl, or C₂ to C₈ Alkyl;

-   R₅=C₁ to C₁₈ alkyl or C₆ to C₁₈ alkyl aryl;

-   M=Alkali Metal, Alkaline Earth Metal, Ammonia, Amine, monoethanol    amine, diethanol amine, triethanol amine, morpholine, imidazole;

-   a=0.01-0.8;

-   b=0.2-0.99;

-   c=0-0.5; and

-   wherein a, b, c represent the mole fraction of each unit and the sum    of a, b, and c, is 1;

-   h) a random copolymer corresponding to the following Formula (V) in    free acid or salt form having the following monomer units and    numbers of monomer units:

-   -   wherein A is selected from the moieties (i) or (ii)    -   (i) —CR₁R₂—CR₃R₄—(ii)

-   -   wherein R₁ and R₃ are selected from substituted benzene, C₁₋₈        alkyl, C₂₋₈ alkenyl, C₂₋₈ alkylcarbonyl, C₁₋₈ alkoxy, carboxyl,        hydrogen, and a ring, R₂ and R₄ are selected from the group        consisting of hydrogen and C₁₋₄ alkyl, wherein R₁ and R₃ can        together with R₂ and/or R₄ when R₂ and/or R₄ are C₁₋₄ alkyl form        the ring;    -   R₇, R₈, R₉, and R₁₀ are individually selected from the group        consisting of hydrogen, C₁₋₆ alkyl, and a C₂₋₈ hydrocarbon        chain, wherein R₁ and R₃ together with R₇ and/or R₈, R₉, and R₁₀        form the C₂₋₈ hydrocarbon chain joining the carbon atoms to        which they are attached, the hydrocarbon chain optionally having        at least one anionic group, wherein the at least one anionic        group is optionally sulfonic;    -   M is selected from the group consisting of hydrogen, and the        residue of a hydrophobic polyalkylene glycol or a polysiloxane,        with the proviso that when A is (ii) and M is the residue of a        hydrophobic polyalkylene glycol, M must be different from the        group —(R₅O)_(m)R₆;    -   R₅ is a C₂₋₈ alkylene radical;    -   R₆ is selected from the group consisting of C₁₋₂₀ alkyl, C₆₋₉        cycloalkyl and phenyl;    -   n, x, and z are numbers from 1 to 100;    -   y is 0 to 100;    -   m is 2 to 1000;    -   the ratio of x to (y+z) is from 1:10 to 10:1 and the ratio of        y:z is from 5:1 to 1:100;

-   i) a copolymer of oxyalkyleneglycol-alkenyl ethers and unsaturated    dicarboxylic acids, comprising:    -   i) 0 to 90 mol % of at least one component of the formula 3a or        3b:

-   -   wherein M is a hydrogen atom, a mono- or divalent metal cation,        an ammonium ion or an organic amine residue, a is 1, or when M        is a divalent metal cation a is ½;    -   wherein X is        -   —OM_(a),        -   —O—(C_(m)H_(2m)O)_(n)—R¹ in which R¹ is a hydrogen atom, an            aliphatic hydrocarbon radical containing from 1 to 20 carbon            atoms, a cycloaliphatic hydrocarbon radical containing 5 to            8 carbon atoms or an optionally hydroxyl, carboxyl, C₁₋₁₄            alkyl, or sulphonic substituted aryl radical containing 6 to            14 carbon atoms, m is 2 to 4, and n is 0 to 100,        -   —NHR₂, —N(R²)₂ or mixtures thereof in which R²=R¹ or            —CO—NH₂; and    -   wherein Y is an oxygen atom or —NR²;    -   ii) 1 to 89 mol % of components of the general formula 4:

-   -   wherein R₃ is a hydrogen atom or an aliphatic hydrocarbon        radical containing from 1 to 5 carbon atoms, p is 0 to 3, and R₁        is hydrogen, an aliphatic hydrocarbon radical containing from 1        to 20 carbon atoms, a cycloaliphatic hydrocarbon radical        containing 5 to 8 carbon atoms or an optionally hydroxyl,        carboxyl, C₁₋₁₄ alkyl, or sulfonic substituted aryl radical        containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to 100,        and    -   iii) 0.1 to 10 mol % of at least one component of the formula 5a        or 5b:

-   -   wherein S is a hydrogen atom or —COOM_(a) or —COOR₅, T is        —COOR₅, —W—R₇, —CO—[—NH—(CH2)3)-]_(s)—W—R₇,        —CO—O—(CH₂)_(z)—W—R₇, a radical of the general formula:

-   -   or —(CH₂)_(z)—V—(CH₂)_(z)—CH═CH—R₁, or when S is —COOR₅ or        —COOM_(a), U₁ is —CO—NHM—, —O— or —CH₂O, U₂ is —NH—CO—, —O— or        —OCH₂, V is —O—CO—C₆H₄—CO—O— or —W—, and W is

-   -   R4 is a hydrogen atom or a methyl radical, R5 is an aliphatic        hydrocarbon radical containing 3 to 20 carbon atoms, a        cycloaliphatic hydrocarbon radical containing 5 to 8 carbon        atoms or an aryl radical containing 6 to 14 carbon atoms, R₆=R₁        or

-   -   R₇=R₁ or

-   -   r is 2 to 100, s is 1 or 2, x is 1 to 150, y is 0 to 15 and z is        0 to 4;    -   iv) 0 to 90 mol % of at least one component of the formula 6a,        6b, or 6c:

-   -   wherein M is a hydrogen atom, a mono- or divalent metal cation,        an ammonium ion or an organic amine residue, a is 1, or when M        is a divalent metal cation a is ½;    -   wherein X is        -   —OM_(a),        -   —O—(C_(m)H_(2m)O)_(n)—R¹ in which R¹ is a hydrogen atom, an            aliphatic hydrocarbon radical containing from 1 to 20 carbon            atoms, a cycloaliphatic hydrocarbon radical containing 5 to            8 carbon atoms or an optionally hydroxyl, carboxyl, C₁₋₁₄            alkyl, or sulphonic substituted aryl radical containing 6 to            14 carbon atoms, m is 2 to 4, and n is 0 to 100,        -   —NH—(C_(m)H_(2m)O)_(n)—R¹,        -   —NHR₂, —N(R²)₂ or mixtures thereof in which R²=R¹ or            —CO—NH₂; and    -   wherein Y is an oxygen atom or —NR²;

-   j) a copolymer of dicarboxylic acid derivatives and oxyalkylene    glycol-alkenyl ethers, comprising:    -   i) 1 to 90 mol. % of at least one member selected from the group        consisting of structural units of formula 7a and formula 7b:

-   -   wherein M is H, a monovalent metal cation, a divalent metal        cation, an ammonium ion or an organic amine;    -   a is ½ when M is a divalent metal cation or 1 when M is a        monovalent metal cation;    -   wherein R¹ is        -   —OM_(a), or        -   —O—(C_(m)H_(2m)O)_(n)—R² wherein R² is H, a C₁₋₂₀ aliphatic            hydrocarbon, a C₅₋₈ cycloaliphatic hydrocarbon, or a C₆₋₁₄            aryl that is optionally substituted with at least one member            selected from the group consisting of COOM_(a), —(SO₃)M_(a),            and —(PO₃)M_(a2);    -   m is 2 to 4;    -   n is 1 to 200;    -   ii) 0.5 to 80 mol. % of the structural units of formula 8:

-   -   wherein R³ is H or a C₁₋₅ aliphatic hydrocarbon;    -   p is 0 to 3;    -   R² is H, a C₁₋₂₀ aliphatic hydrocarbon, a C₅₋₈ cycloaliphatic        hydrocarbon, or a C₆₋₁₄ aryl that is optionally substituted with        at least one member selected from the group consisting of        —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2);    -   m is 2 to 4;    -   n is 1 to 200;    -   iii) 0.5 to 80 mol. % structural units selected from the group        consisting of formula 9a and formula 9b:

-   -   wherein R⁴ is H, C₁₋₂₀ aliphatic hydrocarbon that is optionally        substituted with at least one hydroxyl group,        —(C_(m)H_(2m)O)_(n)—R², —CO—NH—R², C₅₋₈ cycloaliphatic        hydrocarbon, or a C₆₋₁₄ aryl that is optionally substituted with        at least one member selected from the group consisting of        —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2);    -   M is H, a monovalent metal cation, a divalent metal cation, an        ammonium ion or an organic amine;    -   a is ½ when M is a divalent metal cation or 1 when M is a        monovalent metal cation;    -   R² is H, a C₁₋₂₀ aliphatic hydrocarbon, a C₅₋₈ cycloaliphatic        hydrocarbon, or a C₆₋₁₄ aryl that is optionally substituted with        at least one member selected from the group consisting of        —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2);    -   m is 2 to 4;    -   n is 1 to 200;    -   iv) 1 to 90 mol. % of structural units of formula 10

-   -   wherein R⁵ is methyl, or methylene group, wherein R⁵ forms one        or more 5 to 8 membered rings with R⁷;    -   R⁶ is H, methyl, or ethyl;    -   R⁷ is H, a C₁₋₂₀ aliphatic hydrocarbon, a C₆₋₁₄ aryl that is        optionally substituted with at least one member selected from        the group consisting of —COOM_(a), —(SO₃)M_(a), and        —(PO₃)M_(a2), a C₅₋₈ cycloaliphatic hydrocarbon, —OCOR⁴, —OR⁴,        and —COOR⁴, wherein R⁴ is H, a C₁₋₂₀ aliphatic hydrocarbon that        is optionally substituted with at least one —OH,        —(C_(m)H_(2m)O)_(n)—R², —CO—NH—R², C₅₋₈ cycloaliphatic        hydrocarbon, or a C₆₋₁₄ aryl residue that is optionally        substituted with a member selected from the group consisting of        —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2).

In formula (e) the word “derived” does not refer to derivatives ingeneral, but rather to any polycarboxylic acid/salt side chainderivatives of oligoalkyleneglycols, polyalcohols and polyalkyleneglycols that are compatible with dispersant properties and do notdestroy the graft polymer.

The preferred substituents in the optionally substituted aryl radical offormula (i), containing 6 to 14 carbon atoms, are hydroxyl, carboxyl,C₁₋₁₄ alkyl, or sulfonate groups.

The preferred substituents in the substituted benzene are hydroxyl,carboxyl, C₁₋₁₄ alkyl, or sulfonate groups.

Set retarding, or also known as delayed-setting or hydration control,admixtures are used to retard, delay, or slow the rate of setting ofconcrete. They can be added to the concrete mix upon initial batching orsometime after the hydration process has begun. Set retarders are usedto offset the accelerating effect of hot weather on the setting ofconcrete, or delay the initial set of concrete or grout when difficultconditions of placement occur, or problems of delivery to the job site,or to allow time for special finishing processes. Most set retardersalso act as low level water reducers and can also be used to entrainsome air into concrete. Lignosulfonates, hydroxylated carboxylic acids,borax, gluconic, tartaric and other organic acids and theircorresponding salts, phosphonates, certain carbohydrates such as sugarsand sugar-acids and mixtures thereof can be used as retardingadmixtures. In one embodiment the admixture composition comprises about0.5% to about 40% set retarder based on the total dry weight of theadmixture composition components. In another embodiment the admixturecomposition comprises about 2% to about 25% set retarder based on thetotal dry weight of the admixture composition components. In anotherembodiment a cementitious composition comprises about 0.002% to about0.2% set retarder by weight of cementitious binder. In a furtherembodiment a cementitious composition comprises about 0.005% to about0.08% set retarder by weight of cementitious binder.

The strength improvement additive is added to hydraulic cement mixes,such as portland cement concretes, grouts and mortars, high aluminacement concretes, grouts and mortars, and dry mixes for making suchconcretes, grouts and mortars in amounts sufficient to increase thecompressive strength of the hydraulic cement mix. The additive is atleast one of poly(hydroxyalkylated)polyethyleneamines,poly(hydroxyalkylated)polyethylenepolyamines,poly(hydroxyalkylated)polyethyleneimines,poly(hydroxyalkylated)polyamines, hydrazines, 1,2-diaminopropane,polyglycoldiamine, poly(hydroxyalkyl)amine and mixtures thereof. In oneembodiment the admixture composition comprises about 0.5% to about 40%strength improvement additive based on the total dry weight of theadmixture composition components. In another embodiment the admixturecomposition comprises about 2% to about 25% strength improvementadditive based on the total dry weight of the admixture compositioncomponents. In another embodiment a cementitious composition comprisesabout 0.0001% to about 0.2% strength improvement additive by weight ofcementitious binder. In a further embodiment a cementitious compositioncomprises about 0.004% to about 0.08% strength improvement additive byweight of cementitious binder.

Illustrative examples of the strength improvement additive include, butare not limited to, N,N,N′-tri-(hydroxyethyl)ethylenediamine,N,N,N′-tri-(hydroxyethyl)diethylenediamine,N,N′-di-(hydroxyethyl)ethylenediamine,N,N′-bis(2-hydroxypropyl)diethylenetriamine,N,N,N′,N′-tetra(hydroxyethyl)ethylenediamine,N,N,N′,N′,N″-penta(hydroxyethyl)diethylenetriamine,N,N′-bis(2-hydroxypropyl)-N,N,N′-tri(hydroxyethyl)diethylenetriamine,poly(hydroxyethyl)polyethyleneimine, di(hydroxyethyl)1,2-diaminopropane,tetra(hydroxyethyl)1,2-diaminopropane, di(hydroxyethyl)hydrazine,tetra(hydroxyethyl)hydrazine, ethoxylated polyglycoldiamine,triisopropanolamine and mixtures thereof.

The poly(hydroxyalkylated)polyethyleneamine can have the followingformula:

-   -   wherein x is 1, 2 or 3 and R is selected from the group        consisting of hydrogen, 2-hydroxyethyl, and 2-hydroxypropyl,        each R can be the same or different, and at least 40% of the R        groups are hydroxyalkyl, with no more than 40% of the R groups        being hydroxypropyl.

The poly(hydroxyalkylated)polyamines can have the following formula:(R′)₂NCH₂CH₂N(R′)₂

-   -   wherein R′ is (CH₂CH₂O)_(y)H, wherein y is 0, 1 or 2, wherein no        more than one-half (½) of the compounds of the formula have y        equal to 0, and each R′ can be the same or different.    -   The derivatives of hydrazine, 1,2-diaminopropane and        polyglycoldiamine can have the following formula:

-   -   wherein R″ is selected from the group consisting of        (CH₂CH₂O)_(y)H and

-   -   wherein X is a covalent bond or a divalent organic radical        selected from the group consisting of CH₂, CH₂CH₂,

-   -   and CH₂CH₂CH₂OCH₂CH₂OCH₂CH₂OCH₂CH₂CH₂; wherein y and v are 0, 1        or 2;    -   wherein w is 0 or 1;    -   wherein v and w cannot both be 0; and wherein no more than        one-half (½) of the R″ are hydrogen.

The poly(hydroxyalkyl)amines can have the following formula:(R³)_(n)H_(q)N

-   -   Where R³ is [(CHR⁴)_(m)(CHR⁴)O]_(p)H    -   where R⁴ is independently H or CH₃    -   where m=1 or 2    -   where n=2 or 3    -   where p=1 or 2    -   where q=3-n    -   and each R³ can be the same or different for example, all        hydroxypropyl, or mixed hydroxyethyl and hydroxypropyl.

An ethoxylated amine commercially available from Union CarbideCorporation under the trademark Ethoxylated Amine HH which whenethoxylated yields a typical analysis of:

-   -   aminoethyl piperazine: 50% to 70% by weight    -   triethylene tetramine: 40% maximum by weight    -   others: balance.

The dosages of the components of the strength improvement composition ofadmixtures, polycarboxylate high range water reducing dispersant, setretarder, and strength improvement additive, are governed by factorssuch as cement type and reactivity, ambient temperature, and concretemixture proportions.

The hydraulic cement comprising the cementitious formulation is selectedfrom the group consisting of portland cement, modified portland cement,or masonry cement, and mixtures thereof. By portland cement is meant allcementitious compositions which have a high content of tricalciumsilicate and includes portland cement and cements that are chemicallysimilar or analogous to portland cement, the specification for which isset forth in ASTM specification C 150-00.

Cementitious materials are materials that alone have hydraulic cementingproperties, and set and harden in the presence of water. Included incementitious materials are ground granulated blast-furnace slag, naturalcement, hydraulic hydrated lime, and combinations of these and othermaterials.

Aggregate can be included in the cementitious formulation to provide formortars which include fine aggregate, and concretes which also includecoarse aggregate. The fine aggregate are materials that almost entirelypass through a Number 4 sieve (ASTM C 125 and ASTM C 33), such as silicasand. The coarse aggregate are materials that are predominantly retainedon a Number 4 sieve (ASTM C 125 and ASTM C 33), such as silica, quartz,crushed round marble, glass spheres, granite, limestone, calcite,feldspar, alluvial sands, sands or any other durable aggregate, andmixtures thereof.

The cementitious composition described herein may contain otheradditives or ingredients and should not be limited to the statedformulations. Cement additives that can be added include, but are notlimited to: set accelerators, air-entraining or air detraining agents,water reducers, corrosion inhibitors, pigments, wetting agents, watersoluble polymers, strength enhancing agents, rheology modifying agents,water repellents, fibers, dampproofing admixtures, gas formers,permeability reducers, pumping aids, fungicidal admixtures, germicidaladmixtures, insecticidal admixtures, finely divided mineral admixtures,alkali-reactivity reducer, bonding admixtures, shrinkage reducingadmixtures, and any other admixture or additive that does not adverselyaffect the properties of the admixture of the present invention.

An accelerator that can be used in the admixture of the presentinvention can include, but is not limited to, a nitrate salt of analkali metal, alkaline earth metal, or aluminum; a nitrite salt of analkali metal, alkaline earth metal, or aluminum; a thiocyanate of analkali metal, alkaline earth metal or aluminum; a thiosulphate of analkali metal, alkaline earth metal, or aluminum; a hydroxide of analkali metal, alkaline earth metal, or aluminum; a carboxylic acid saltof an alkali metal, alkaline earth metal, or aluminum (such as calciumformate); a halide salt of an alkali metal or alkaline earth metal (suchas bromide), Examples of accelerators particularly suitable for use inthe present invention include, but are not limited to, POZZOLITH® NC534,nonchloride type accelerator and/or RHEOCRETE® CNI calcium nitrite-basedcorrosion inhibitor both sold under the trademarks by Master BuildersInc. of Cleveland, Ohio.

The salts of nitric acid have the general formula M(NO₃)_(a) where M isan alkali metal, or an alkaline earth metal or aluminum, and where a is1 for alkali metal salts, 2 for alkaline earth salts, and 3 for aluminumsalts. Preferred are nitric acid salts of Na, K, Mg, Ca and Al.

Nitrite salts have the general formula M(NO₂)_(a) where M is an alkalimetal, or an alkaline earth metal or aluminum, and where a is 1 foralkali metal salts, 2 for alkaline earth salts, and 3 for aluminumsalts. Preferred are nitric acid salts of Na, K, Mg, Ca and Al.

The salts of the thiocyanic acid have the general formula M(SCN)_(b),where M is an alkali metal, or an alkaline earth metal or aluminum, andwhere b is 1 for alkali metal salts, 2 for alkaline earth salts and 3for aluminum salts. These salts are variously known as sulfocyanates,sulfocyanides, rhodanates or rhodanide salts. Preferred are thiocyanicacid salts of Na, K, Mg, Ca and Al.

The thiosulfate salts have the general formula M_(f)(S₂O₃)_(g) where Mis alkali metal or an alkaline earth metal or aluminum, and f is 1 or 2and g is 1, 2 or 3, depending on the valencies of the M metal elements.Preferred are thiosulfate acid salts of Na, K, Mg, Ca and Al.

The carboxylic acid salts have the general formula RCOOM wherein R is Hor C₁ to about C₁₀ alkyl, and M is alkali metal or an alkaline earthmetal or aluminum. Preferred are carboxylic acid salts of Na, K, Mg, Caand Al. A preferred carboxylic acid salt is calcium formate.

The term air entrainer includes any chemical that will entrain air incementitious compositions. Air entrainers can also reduce the surfacetension of a composition at low concentration. Air-entraining admixturesare used to purposely entrain microscopic air bubbles into concrete.Air-entrainment dramatically improves the durability of concrete exposedto moisture during cycles of freezing and thawing. In addition,entrained air greatly improves a concrete's resistance to surfacescaling caused by chemical deicers. Air entrainment also increases theworkability of fresh concrete while eliminating or reducing segregationand bleeding. Materials used to achieve these desired effects can beselected from wood resin, sulfonated lignin, petroleum acids,proteinaceous material, fatty acids, resinous acids, alkylbenzenesulfonates, sulfonated hydrocarbons, vinsol resin, anionic surfactants,cationic surfactants, nonionic surfactants, natural rosin, syntheticrosin, an inorganic air entrainer, synthetic detergents, and theircorresponding salts, and mixtures thereof. Air entrainers are added inan amount to yield a desired level of air in a cementitious composition.Generally, the amount of air entrainers (about 5% to about 15% solidscontent) in a cementitious composition ranges from about 0.07 ml toabout 3.9 ml per kilogram of dry cement. In one embodiment the dosage isabout 0.33 ml to about 0.98 ml per kilogram of dry cement. Weightpercentages of the primary active ingredient of the air entrainers,wherein the primary active ingredient in the air entrainer provides thedesired effect i.e., entrainment of air in the cementitious composition,are about 0.001% to about 0.05%; based on the weight of dry cementitiousmaterial. But this can vary widely due to variations in materials, mixproportion, temperature, and mixing action. An air entrainer useful withthe present admixture composition can be any known air entrainer forcement, including natural resin, synthetic resin, and mixtures thereof.Examples of air entrainers that can be utilized in the present inventioninclude, but are not limited to MB AE 90, MB VR and MICRO AIR®, allavailable from Master Builders Inc. of Cleveland, Ohio.

Air detrainers are used to decrease the air content in the cementitiouscomposition. Examples of air detrainers that can be utilized in thepresent invention include, but are not limited to tributyl phosphate,dibutyl phthalate, octyl alcohol, water-insoluble esters of carbonic andboric acid, acetylenic diols, ethylene oxide-propylene oxide blockcopolymers and silicones.

Corrosion inhibitors in concrete serve to protect embedded reinforcingsteel from corrosion. The high alkaline nature of the concrete causes apassive and non-corroding protective oxide film to form on the steel.However, carbonation or the presence of chloride ions from deicers orseawater, together with oxygen can destroy or penetrate the film andresult in corrosion. Corrosion-inhibiting admixtures chemically slowthis corrosion reaction. The materials most commonly used to inhibitcorrosion are calcium nitrite, sodium nitrite, sodium benzoate, certainphosphates or fluorosilicates, fluoroaluminates, amines, organic basedwater repelling agents, and related chemicals.

Dampproofing admixtures reduce the permeability of concrete that has lowcement contents, high water-cement ratios, or a deficiency of fines inthe aggregate portion. These admixtures retard moisture penetration intodry concrete and include certain soaps, stearates, and petroleumproducts.

Permeability reducers are used to reduce the rate at which water underpressure is transmitted through concrete. Silica fume, fly ash, groundslag, metakaolin, natural pozzolans, water reducers, and latex can beemployed to decrease the permeability of the concrete.

Pumping aids are added to concrete mixes to improve pumpability. Theseadmixtures thicken the fluid concrete, i.e., increase its viscosity, toreduce de-watering of the paste while it is under pressure from thepump. Among the materials used as pumping aids in concrete are organicand synthetic polymers, hydroxyethylcellulose (HEC) or HEC blended withdispersants, organic flocculents, organic emulsions of paraffin, coaltar, asphalt, acrylics, bentonite and pyrogenic silicas, naturalpozzolans, fly ash and hydrated lime.

Bacteria and fungal growth on or in hardened concrete may be partiallycontrolled through the use of fungicidal, germicidal, and insecticidaladmixtures. The most effective materials for these purposes arepolyhalogenated phenols, dialdrin emulsions, and copper compounds.

Finely divided mineral admixtures are materials in powder or pulverizedform added to concrete before or during the mixing process to improve orchange some of the plastic or hardened properties of portland cementconcrete. Portland cement, as used in the trade, means a hydrauliccement produced by pulverizing clinker, comprising hydraulic calciumsilicates, calcium aluminates, and calcium aluminoferrites, and usuallycontaining one or more of the forms of calcium sulfate as an intergroundaddition. Portland cements are classified in ASTM C 150 as Type I II,III, IV, or V. The finely divided mineral admixtures can be classifiedaccording to their chemical or physical properties as: cementitiousmaterials; pozzolans; pozzolanic and cementitious materials; andnominally inert materials.

A pozzolan is a siliceous or aluminosiliceous material that possesseslittle or no cementitious value but will, in the presence of water andin finely divided form, chemically react with the calcium hydroxideproduced during the hydration of portland cement to form materials withcementitious properties. Diatomaceous earth, opaline cherts, clays,shales, fly ash, silica fume, volcanic tuffs and pumicites are some ofthe known pozzolans. Certain ground granulated blast-furnace slags andhigh calcium fly ashes possess both pozzolanic and cementitiousproperties. Natural pozzolan is a term of art used to define thepozzolans that occur in nature, such as volcanic tuffs, pumices,trasses, diatomaceous earths, opaline, cherts, and some shales.Nominally inert materials can also include finely divided raw quartz,dolomites, limestones, marble, granite, and others. Fly ash is definedin ASTM C618.

Alkali-reactivity reducers can reduce the alkali-aggregate reaction andlimit the disruptive expansion forces that this reaction can produce inhardened concrete. Pozzolans (fly ash, silica fume), blast-furnace slag,salts of lithium and barium are especially effective.

Bonding admixtures are usually added to portland cement mixtures toincrease the bond strength between old and new concrete and includeorganic materials such as rubber, polyvinyl chloride, polyvinyl acetate,acrylics, styrene butadiene copolymers, and other powdered polymers.

Fresh concrete can sometimes be harsh because of faulty mixtureproportions or certain aggregate characteristics such as particle shapeand improper grading. Under these conditions, entrained air, which actslike a lubricant, can be used as a workability improving agent. Otherworkability agents include certain water reducing admixtures, someviscosity modifying admixtures and certain finely divided admixtures.

In the construction field, many methods of protecting concrete fromtensile stresses and subsequent cracking have been developed through theyears. One modern method involves distributing fibers throughout a freshconcrete mixture. Upon hardening, this concrete is referred to asfiber-reinforced concrete. Fibers can be made of zirconium materials,carbon, steel, fiberglass, or synthetic materials, e.g., polypropylene,nylon, polyethylene, polyester, rayon, high-strength aramid, or mixturesthereof.

The shrinkage reducing agent which can be used in the present inventioncan include but is not limited to RO(AO)₁₋₁₀H, wherein R is a C₁₋₅ alkylor C₅₋₆ cycloalkyl radical and A is a C₂₋₃ alkylene radical, alkalimetal sulfate, alkaline earth metal sulfates, alkaline earth oxides,preferably sodium sulfate and calcium oxide. TETRAGUARD® shrinkagereducing agent is preferred and is available from Master Builders Inc.of Cleveland, Ohio.

Natural and synthetic admixtures are used to color concrete foraesthetic and safety reasons. These coloring admixtures are usuallycomposed of pigments and include carbon black, iron oxide,phthalocyanine, umber, chromium oxide, titanium oxide and cobalt blue.

Examples of inventive strength improvement admixture compositions weretested for the effect of their addition on the compressive strength andsetting time of concrete mixtures.

Tables 1-9 show the effect of various retarder chemistries and strengthimprovement additive additions to cementitious mixtures containingpolycarboxylate dispersant. Concrete mixture proportions for theexamples were determined according to the guidelines outlined in ACI211.1-91, Standard Practice for Selecting Proportions for Normal WeightConcrete. The mix design was based on a nominal cement content of 517lb/yd³ using a Type I portland cement (Tables 1, 3, 5, 6, and 8). Tables2, 4, and 7 had 15% by weight of the Type I portland cement replacedwith fly ash. Tests for slump (ASTM C 143), air content (ASTM C 231),compressive strength (ASTM C 39) and time of set (ASTM C 403) wereperformed in accordance with ASTM procedures.

Of particular interest was the effect on setting time and compressivestrengths, both between the different set retarder chemistries at lowand high levels and in the presence of the strength improvementadmixture.

For Tables 1 and 2 each component was added separately to the mixer in apartial charge of mixing water prior to the batching of solidingredients. Tributyl phosphate (TBP), or solubilized tributyl phosphateusing an amine solubilizing agent in Table 2, were also added separatelyat 0.01% cwt so that air contents would be low (<3%) and similar.Tributyl phosphate or solubilized tributyl phosphate was added at0.0096% cwt to mixtures in Table 2. Concrete materials were batched andmixed for 5 minutes.

TABLE 1 Sample S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 S-9 S-10 S-11 Cement 516512 515 518 518 518 518 518 518 518 519 (lbs/yd3) Sand (lbs/yd3) 13471386 1395 1403 1403 1404 1403 1403 1402 1402 1405 Stone (lbs/yd3) 18661922 1935 1946 1946 1947 1946 1946 1944 1944 1948 Water (lbs/yd3) 301267 258 248 250 246 250 250 250 251 250 Water/Cement 0.583 0.521 0.5010.479 0.483 0.475 0.483 0.483 0.483 0.485 0.482 Sand/Aggregate 0.43 0.430.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 % Water 11.30 14.29 17.6116.94 18.27 16.94 16.94 16.94 16.61 16.94 Reduction PC disp (% cwt) 0.100.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Polysaccharide — 0.05 0.08— — — — — 0.05 — (% cwt) Na Gluconate/ — — — 0.04 0.06 — — — — 0.04Gluconic Acid (% cwt) Gluconic Acid — — — — — 0.04 0.06 — — — (% cwt)SIA (% cwt) — — — — — — — 0.04 0.04 0.04 Slump (in) 5.00 4.00 6.25 4.007.00 4.00 4.00 6.75 2.75 6.75 6.25 % Air 2.0 2.0 2.0 2.1 2.0 2.2 2.0 2.02.1 2.0 1.9 Initial Set Time 4.50 4.42 5.75 7.08 6.08 6.83 6.17 7.924.72 5.58 6.25 (hrs) Compressive Strength  1 Day 1540 2260 2330 24402410 2640 2570 2340 2500 2540 2440  7 day 3540 4440 4950 5310 5190 54305170 5150 5450 5560 5950 28 Day 5000 5980 5740 6810 6520 6790 6610 67206950 7320 7890 PC Disp—polycarboxyate dispersant SIA—strengthimprovement additive

Table 1 shows the setting time and late age compressive strength (28Day) effect of three commonly used set retarder chemistries: apolysaccharide mixture, a hydroxycarboxylic acid, and a 65:35 blend ofsodium gluconate/hydroxycarboxylic acid on concrete mixtures. In samplesS-3 to S-8 the set retarders were used at a low (0.04-0.05% cwt) and ahigh level (0.06-0.08% cwt) in combination with a polycarboxylatedispersant. For all of the concrete mixtures in the table, thepolycarboxylate dispersant level was held constant at 0.1% by cementweight. In samples S-3 to S-8, both setting time and 28 day compressivestrength were found to increase as the set retarder level increased(mixes S-3 vs. S-4, S-5 vs. S-6, S-7 vs. S-8) and except for the sample(S-3) with the low level of polysaccharide, all of the concrete mixtureshad retarded setting times and higher compressive strengths relative tothe polycarboxylate dispersant only reference (S-2). The concretemixture containing the strength improvement additive (SIA) as the onlyaddition to the polycarboxylate dispersant (S-9) also showed a slightincrease in setting time and an increase in compressive strengthrelative to the polycarboxylate dispersant only concrete mixture. Anunexpected additional increase in compressive strength over thepolycarboxylate dispersant plus set retarder concrete mixtures (S-3 toS-8) or polycarboxylate dispersant plus strength improvement combination(S-9) was found for the three component combination (S-10 and S-11) ofpolycarboxylate dispersant, strength improvement additive and low levelsof either the polysaccharide or sodium gluconate/hydroxycarboxylicblend. The increase in compressive strength of the concrete mixturescontaining the three components (polycarboxylate dispersant, strengthimprovement additive, and set retarder) was observed with only a smallchange in setting time relative to the polycarboxylate dispersant plusset retarder (S-10 vs. S-3 and S-11 vs. S-5 and S-7). The resultsdemonstrate that the increase in compressive strength is the result of achemical effect on cement hydration and is not the result of improvedwater reduction (decrease in water to cement ratio).

TABLE 2 Sample S-12 S-13 S-14 S-15 S-16 S-17 S-18 S-19 Cement (lbs/yd3)445 441 439 443 444 443 444 444 Class F ash (lbs/yd3) 80 79 79 79 80 8080 80 Sand (lbs/yd3) 1357 1381 1373 1385 1388 1387 1390 1390 Stone(lbs/yd3) 1882 1913 1902 1918 1923 1921 1925 1925 Water (lbs/yd3) 293262 260 260 256 252 253 253 Water/Cement 0.558 0.504 0.502 0.498 0.4890.482 0.483 0.483 Sand/Aggregate 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43PC Disp (% cwt) — 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Solubilized TBP — —0.0096 — — — — — (% cwt) TBP (% cwt) — 0.0096 — 0.0096 0.0096 0.00960.0096 0.0096 Polysaccharide (% cwt) — — — 0.040 — — 0.040 — NaGluconate/ — — — — 0.032 — — 0.032 Gluconic Acid (% cwt) SIA (% cwt) — —— — — 0.032 0.032 0.032 Slump (in) 7.00 7.00 6.75 8.00 7.75 7.25 7.758.00 % Air 1.3 2.0 2.6 1.9 1.9 2.2 2.0 2.0 Initial Set Time (hrs) 5.335.58 5.75 6.67 6.83 5.75 6.75 7.17 Compressive Strength  1 Day 1140 17401800 1740 1750 1730 1750 1760  7 Day 2680 3650 3700 3870 4090 4070 44104350 28 Day 3940 5000 4900 5400 5580 6050 6280 6470 PCDisp—polycarboxylate dispersant SIA—strength improvement additiveTBP—tributyl phosphate

Table 2 contains concrete mixtures where 15% (by weight) of cement wasreplaced with fly ash and shows similar comparisons of polycarboxylatedispersant only compared to combinations of polycarboxylate dispersantand set retarder, polycarboxylate dispersant and strength improvementadditive, and polycarboxylate dispersant in combination with strengthimprovement additive and a set retarder. The levels of each component inthe concrete mixtures were lower but proportional to the concretemixtures in Table 1. Similar to the results in Table 1, an unexpectedincrease in compressive strength with only a small change in settingtime was observed for the three component combination compared to thepolycarboxylate dispersant plus set retarder or strength improvementadditive concrete mixtures (mixes S-15 vs. S-18 and S-16 vs. S-19).

In Tables 3 and 4 admixture solutions were first prepared containing allof the components to be tested (polycarboxylate dispersant, strengthimprovement additive, solubilized tributyl phosphate, and/or setretarder). This solution was added up front to the concrete mixtureswith a partial charge of mixing water. The level of tributyl phosphatein solutions shown in Table 3 is proportional (by weight ofpolycarboxylate dispersant) to that shown in Tables 1 and 2. Thetributyl phosphate level for solutions shown in Table 4 is approximately33% lower (by weight of polycarboxylate dispersant) to that shown inTables 1 and 2.

TABLE 3 Sample S-20 S-21 S-22 S-23 S-24 S-25 S-26 S-27 S-28 Cement(lbs/yd3) 522 512 518 518 516 509 507 507 509 Sand (lbs/yd3) 1347 13401357 1355 1351 1383 1377 1378 1384 Stone (lbs/yd3) 1887 1876 1900 18971892 1936 1928 1930 1938 Water (lbs/yd3) 307 287 268 277 284 240 239 239257 Water/Cement 0.588 0.561 0.517 0.535 0.550 0.472 0.471 0.471 0.505Sand/Aggregate 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 % WaterReduction 6.51 12.70 9.77 7.49 21.82 22.15 22.15 16.29 PC Disp — 0.0340.034 0.034 0.034 0.1021 0.1021 0.1021 0.100 Na Gluconate/ — — 0.00880.0044 0.0088 0.0265 0.0133 0.0265 — Gluconic Acid (% cwt) Gluconic Acid(% cwt) — — 0.0155 0.0024 0.0048 0.0460 0.0071 0.0143 — SIA (% cwt) — —0.0136 0.0068 0.0136 0.0408 0.0204 0.0408 — Slump (in) 7.50 7.25 7.507.50 7.00 7.50 7.75 7.75 7.00 % Air 1.1 2.9 3.0 2.6 2.4 3.5 3.9 3.8 2.4Initial Set Time 5.0 5.6 5.8 6.3 5.5 10.8 5.9 6.4 5.4 CompressiveStrength  1 day 1530 1910 2030 1800 2200 2130 2720 2560 2350  7 day 35003990 4510 4100 4770 5850 5250 5600 4660 28 day 4840 5220 5780 5390 60707270 6530 7160 5830 PC Disp—polycarboxyate dispersant SIA—strengthimprovement additive

Table 3 shows setting time and strength data for different blend ratiosof sodium gluconate/hydroxycarboxylic acid set retarders in combinationwith the strength improvement additive and polycarboxylate dispersantcompared to polycarboxylate dispersant alone. The sodiumgluconate/hydroxycarboxylic acid blend ratios are 23.5:76.5 (S-22) and42:58 (S-23 and S-24). The results show that with a low level ofpolycarboxylate dispersant, all of the three component combinations ofset retarder/strength improvement additive/polycarboxylate dispersantgave higher 28 day compressive strengths with minimal change in settingtime versus the polycarboxylate dispersant only reference (mixes S-22,S-23, S-24 vs. S-21). At the higher polycarboxylate dispersant level,the concrete mixture containing the highest level of gluconic acid(S-25) showed an increase in setting time as well as a compressivestrength increase relative to the polycarboxylate dispersant onlyreference (S-28). The other concrete mixtures having the three componentcombination (S-26 and S-27) showed an increase in compressive strengthwith a minimal change in setting time compared to the polycarboxylateonly reference (S-28).

TABLE 4 Sample S-29 S-30 S-31 S-32 S-33 S-34 S-35 S-36 S-37 S-38 S-39Cement 439 435 434 434 435 435 434 434 434 434 434 (lbs/yd3) Class F Ash79 78 78 78 78 78 78 78 78 78 78 (lbs/yd3) Sand (lbs/yd3) 1400 1402 14011399 1402 1402 1425 1426 1427 1425 1426 Stone (lbs/yd3) 1808 1812 18101809 1812 1812 1841 1842 1843 1841 1842 Water (lbs/yd3) 316 296 296 290292 290 279 274 271 269 271 Water/Cement 0.610 0.577 0.578 0.566 0.5690.565 0.545 0.535 0.529 0.525 0.529 Sand/Aggregate 0.45 0.45 0.45 0.450.45 0.45 0.45 0.45 0.45 0.45 0.45 % Water 6.33 6.33 8.23 7.59 8.2311.71 13.29 14.24 14.87 14.24 Reduction PC Disp — 0.037 0.037 0.0370.037 0.037 0.100 0.100 0.100 0.100 0.100 Polysaccharide — — — — —0.0088 — — — — 0.0265 (% cwt) Gluconic Acid — — 0.0133 0.0133 0.01330.0048 — 0.0400 0.0400 0.0400 0.0143 (% cwt) SIA — — — 0.0133 0.00830.0133 — — 0.0400 0.0250 0.0400 Slump (in) 6.00 5.00 6.50 6.00 6.50 5.756.25 7.00 6.50 7.00 5.75 % Air 1.1 2.2 2.3 2.7 2.5 2.6 2.1 2.4 2.5 2.72.5 Initial Set (hrs) 5.8 6.1 6.6 6.5 6.4 6.7 6.3 8.6 9.0 9.0 8.3Compressive Strength  1 Day 1060 1230 1160 1310 1270 1260 1550 1240 11801270 1170  7 Day 2930 3240 3170 3310 3330 3200 3590 3320 3820 3960 395028 Day 4250 4640 4430 5050 4930 4920 5200 4890 5750 5980 5970 PCDisp—polycarboxylate dispersant SIA—strength improvement additive

Table 4 contains concrete mixtures where 15% (by weight) of cement wasreplaced with fly ash and shows comparisons of polycarboxylatedispersant only to combinations of polycarboxylate dispersant and setretarder and polycarboxylate dispersant, set retarder and strengthimprovement additive. At the low polycarboxylate dispersant level, thethree component combination of polycarboxylate dispersant, strengthimprovement additive and set retarder (S-32, S-33, S-34) showed anincrease in compressive strength with only a small change in settingtime compared to the polycarboxylate dispersant only reference (S-30).No difference in setting time was observed for the three componentcombination (S-32, S-33, S-34) as compared to the polycarboxylatedispersant plus set retarder (S-31). At the high polycarboxylatedispersant level, mixtures containing the three component combination(S-37, SS-38, S-39), showed increased compressive strength and minimalchange in setting time relative to the polycarboxylate dispersant plusset retarder concrete mixture (S-36).

For Tables 5, 6, 7, 8 and 9 each component was added separately to themixer in a partial charge of mixing water prior to the batching of solidingredients. Tributyl phosphate (TBP) was also added separately at0.0005% cwt to the mixtures in Table 5 so that air contents would be low(<3%) and similar. Concrete materials were batched and mixed for 5minutes.

TABLE 5 Sample S-40 S-41 S-42 S-43 S-44 S-45 S-46 S-47 S-48 S-49 Cement518 515 515 518 517 517 517 516 518 515 (lbs/yd3) Sand (lbs/yd3) 13501377 1377 1384 1382 1383 1383 1379 1382 1378 Stone (lbs/yd3) 1850 18871887 1897 1894 1896 1896 1891 1893 1889 Water (lbs/yd3) 306 269 269 271265 265 265 269 265 268 % Water 12.09 12.09 11.44 13.40 13.40 13.4012.09 13.40 12.42 Reduction PC Disp 0.080 0.080 0.080 0.080 0.080 0.0800.080 0.080 0.080 (% cwt) HA (% cwt) 0.020 0.020 0.020 0.020 PA (% cwt)0.010 0.010 0.010 0.010 SIA (% cwt) 0.010 0.020 0.040 0.010 0.020 0.040TBP (% cwt) 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 Slump(in) 7.50 7.25 7.75 8.00 7.25 8.00 7.75 8.00 7.50 8.00 % Air 1.8 2.6 2.62.1 2.6 2.5 2.5 2.5 2.6 2.6 Initial Set Time 5.08 5.67 6.67 6.67 6.586.50 7.00 6.75 6.50 6.75 (Hrs.) Compressive Strength  7 Day 3870 43604880 4730 5110 5160 4840 3910 5080 5100 28 Day 5170 6020 6360 6570 70407490 6390 6680 6960 6660 PC Disp—polycarboxyate dispersant SIA—strengthimprovement additive TBP—tributyl phosphate HA—alpha hydroxycarboxylicacid PA—phosphonic acid salt

Table 5 shows the setting time and late age compressive strength (28day) effect of two other commonly used retarder chemistries: alphahydroxycarboxylic acid, and a phosphonic acid salt on concrete mixtures.For all of the concrete mixtures in the table, the polycarboxylatedispersant level was held constant at 0.08% by cement weight and thelevel of each set retarder was selected to retard setting times byapproximately 1.5 to 2.0 hours. Samples S-42 and S-46 show each of theset retarders in combination with a polycarboxylate dispersant andsamples S-43 to S-45 and S-47 to S-49 show the combination ofpolycarboxylate dispersant and HA set retarder with increasing levels ofSIA. Relative to the polycarboxylate only reference (S-41), addition ofset retarder (S-42 and S-46) increased 28-day compressive strengths.Samples S-43 to S-45 show an increase in 28-day compressive strengthover the polycarboxylate plus set retarder (S-42 and S-46) without anychange in setting time. Samples S-43 to S-45 demonstrate that increasingamounts of SIA produced increasing compressive strength in thecementitious mixtures. Samples S-47 to S-49 also show an increase incompressive strength for the three component combination ofpolycarboxylate, PA set retarder and SIA with a slight reduction insetting time. Similar to the results shown in Table 1, the increase incompressive strength appears to be the result of a chemical effect oncement hydration and is not the result of improved water reduction(decrease in water to cement ratio).

The examples shown in Tables 6 and 7 demonstrate the synergy of a setretarder plus SIA in combination with a polycarboxylate compared toother dispersant types such as lignosulfonate and sulfonated naphthaleneformaldehyde condensate (BNS). The mixtures in Table 6 use portlandcement while Table 7 contains concrete mixtures where 15% (by weight) ofcement was replaced with fly ash. In Table 6, each dispersant level wasselected to provide the same level of water-reduction and mix watercontents were held constant for each mixture where set retarder or SIAwas additionally added. TBP was added to the BNS and polycarboxylatemixtures to keep air contents below 2.5%. The level of set retarder andSIA in these examples was fixed at 0.03% by cement weight. In Table 7,each dispersant level was lowered relative to those in Table 6 in orderto maintain the same level of water reduction with the portland cementplus fly ash mixture. Mix water contents were held constant for eachmixture where set retarder or SIA was additionally added. TBP was addedto the BNS and polycarboxylate mixtures to keep air contents below 2.5%.The proportion of set retarder to the dispersant in Table 7 is the sameas in Table 6 and the SIA in these examples was fixed at 0.035% bycement weight.

Samples S-60 to S-62 in Table 6, show the setting times and compressivestrength for calcium BNS, sodium lignosulfonate and polycarboxylatedispersants and samples S-51 to S-53 show each dispersant with added setretarder. Relative to their respective dispersant only references, theaddition of set retarder shows 28-day compressive strengths were thesame or slightly reduced and setting times were increased byapproximately one hour for the polycarboxylate dispersant, and two hoursfor the BNS and lignosulfonate. Samples S-57 to S-59 show eachdispersant with added SIA. Relative to their respective references, theaddition of SIA shows 28-day compressive strengths were increased andsome increase in setting time was observed for the BNS andlignosulfonate dispersants. Samples S-54 to S-56 show each dispersantwith both set retarder and SIA additions. With the BNS dispersant,28-day compressive strengths were the same as those with SIA only andsetting time increased an additional one-hour relative to the BNS plusretarder combination. With the lignosulfonate dispersant, 28-daycompressive strengths were lower than those with SIA only and thesetting time increased approximately one hour relative to thelignosulfonate dispersant plus retarder combination. For thepolycarboxylate dispersant, a significant increase in 28-day compressivestrengths was observed relative to the polycarboxylate plus retarder orpolycarboxylate plus SIA without a significant change in setting time.

TABLE 6 Sample S-50 S-51 S-52 S-53 S-54 S-55 S-56 S-57 S-58 S-59 S-60S-61 S-62 Cement (lbs/yd3) 518 517 519 519 517 518 519 515 517 519 516517 520 Sand (lbs/yd3) 1350 1386 1393 1393 1387 1388 1393 1382 1387 13931383 1387 1394 Stone (lbs/yd3) 1852 1900 1909 1910 1902 1904 1910 18941902 1910 1896 1902 1912 Water (lbs/yd3) 310 268 261 269 268 260 269 267260 269 267 260 269 % Water 13.55 15.81 13.23 13.55 16.13 13.23 13.8716.13 13.23 13.87 16.13 13.23 Reduction Lignosulfonate 0.280 0.280 0.2800.280 (% cwt) BNS (% cwt) 0.430 0.430 0.430 0.430 PC Disp (% cwt) 0.1100.110 0.110 0.110 Na 0.030 0.030 0.030 0.030 0.030 0.030 Gluconate/G.A.(% cwt) SIA (% cwt) 0.030 0.030 0.030 0.030 0.030 0.030 TBP (% cwt)0.005 0.010 0.005 0.010 0.005 0.010 0.005 0.010 Slump (in) 8.00 6.758.00 8.00 5.75 8.00 8.25 4.50 8.00 8.00 4.50 6.00 8.00 % Air 1.5 2.2 2.21.7 2.1 2.5 1.7 2.5 2.6 1.7 2.4 2.6 1.6 Initial Set (Hrs.) 4.75 9.927.83 6.50 11.00 8.67 6.83 8.17 6.33 5.67 7.83 5.67 5.42 CompressiveStrength  7 Day 3890 4770 4710 4790 5120 5460 5070 5320 4900 5180 46504680 4620 28 Day 4860 6040 5670 5850 6730 6210 6770 6840 6470 6270 61205960 5900 BNS—napthalene sufonate PC Disp—polycarboxylate dispersantSIA—strength improvement additive TBP—tributyl phosphate NaGluconate/G.A.—sodium gluconate gluconic acid blend

TABLE 7 Sample S-63 S-64 S-65 S-66 S-67 S-68 S-69 S-70 S-71 S-72 S-73S-74 S-75 Cement 517 510 515 511 510 513 511 510 512 510 510 514 510(lbs/yd3) Class F 81 80 81 80 80 80 80 80 80 80 80 80 80 Ash (lbs/yd3)Sand 1309 1343 1354 1344 1343 1350 1344 1341 1347 1341 1341 1351 1341(lbs/yd3) Stone 1788 1833 1848 1835 1833 1843 1835 1831 1839 1831 18311845 1831 (lbs/ yd3) Water 330 281 284 281 281 283 281 281 282 281 281283 281 (lbs/yd3) % Water 14.85 13.94 14.85 14.85 14.24 14.85 14.8514.55 14.85 14.85 14.24 14.85 Reduction Sodium 0.242 0.242 0.242 0.242Lignin (% cwt) BNS 0.346 0.346 0.346 0.346 (% cwt) PC Disp 0.095 0.0950.095 0.095 (% cwt) Na Gluc/ 0.026 0.026 0.026 0.026 0.026 0.026 G.A (%cwt) SIA 0.035 0.035 0.035 0.035 0.035 0.035 (% cwt) TBP 0.0043 0.00860.0043 0.0086 0.0043 0.0086 0.0043 0.0086 (% cwt) Slump 7.25 7.00 8.007.75 7.25 8.00 8.00 7.50 7.75 7.00 7.25 8.00 7.50 (in) % Air 0.9 2.2 1.42.1 2.2 1.7 2.1 2.3 1.9 2.3 2.3 1.6 2.3 Initial 5.83 10.25 7.75 6.5010.67 8.75 6.58 9.50 6.83 5.42 8.83 6.00 5.42 Set (Hrs.) CompressiveStrength  7 Day 3950 4500 4600 4500 4740 4880 5190 5080 4980 5180 44904470 4480 28 Day 5420 5980 5990 6180 6650 6540 6990 6910 6860 6830 59105870 6060 BNS—naphalene sulfonate PC Disp—polycarboxylate dispersantSIA—strength improvement additive TBP—tributyl phosphate NaGluc/G.A.—sodium gluconate gluconic acid blend

The comparative examples in Table 7 demonstrate the same performancetrends with the portland cement plus fly ash mixtures as observed inTable 6. Relative to their respective dispersant only references (S-73to S-75), samples S-64 to S-66, dispersant with added set retarder, show28-day compressive strengths were the same and setting times wereincreased by approximately one hour for the samples containingpolycarboxylate, and 1.5 hours for the BNS and lignosulfonate. SamplesS-70 to S-72 show cementitious mixtures containing each dispersant type(polycarboxylate, BNS and lignosulfonate) with added SIA. Relative totheir respective references, 28-day compressive strengths increased andsome increase in setting time was observed for the samples containingBNS and lignosulfonate dispersants.

Samples S-67 to S-69 are mixtures containing the dispersant types withboth set retarder and SIA additions. S-68, with the BNS dispersant, had28-day compressive strengths that were lower than those of S-71 with BNSand SIA only and setting time increased an additional one hour relativeto the BNS, plus retarder combination of S-65. With the lignosulfonatedispersant, 28-day compressive strengths were lower than those with SIA(S-70) only and the setting time increased approximately one hourrelative to the lignosulfonate dispersant plus retarder combination ofS-64. For the polycarboxylate dispersant, 28-day compressive strengthswere increased relative to S-66 polycarboxylate plus retarder or S-71polycarboxylate plus SIA without a significant change in setting time.

Mixtures in Table 8 were prepared using combinations of apolycarboxylate dispersant, a set retarder, SIA and solubilized TBP withan amine solubilizing agent. These combinations were added to theconcrete at low, medium, and high dosage levels where the high level wasselected to impart a high degree of set retardation. A commerciallyavailable set accelerating admixture, NC534 from Master Builders, wasadditionally added at 15 fl.oz./cwt. with the low and medium examplelevels and at 30 fl.oz./cwt with the medium and high example levels. Ofinterest was the effect of reducing or eliminating set retardation andthe influence on late age compressive strength.

TABLE 8 Sample S-76 S-77 S-78 S-79 S-80 S-81 S-82 S-83 Cement (lbs/yd3)517 519 516 514 515 516 517 515 Sand (lbs/yd3) 1356 1407 1390 1370 13871375 1402 1387 Stone (lbs/yd3) 1867 1934 1913 1887 1909 1893 1928 1909Water (lbs/yd3) 305 248 256 266 255 267 247 255 % Water Reduction 18.6916.07 12.79 16.39 12.46 19.02 16.39 PC Disp (% cwt) 0.162 0.122 0.0810.122 0.081 0.162 0.122 Na Gluconate/G.A (% cwt) 0.056 0.042 0.028 0.0420.028 0.056 0.042 SIA (% cwt) 0.034 0.026 0.017 0.026 0.017 0.034 0.026TBP (% cwt) 0.014 0.011 0.007 0.011 0.007 0.014 0.011 Pozzolith NC 53415 15 30 30 (fl.oz/cwt) Slump (in) 6.00 7.00 6.75 6.25 6.75 7.00 7.007.00 % Air 1.5 2.3 2.7 3.1 2.9 2.8 2.6 2.9 Initial Set (Hrs.) 5.67 9.588.58 7.25 6.50 5.50 6.17 5.42 Compressive Strength  7 Day 4130 6070 55705100 5980 5390 6310 5970 28 Day 5470 7660 7220 7120 7680 7520 7760 7170PC Disp—polycarboxylate dispersant SIA—strength improvement additiveTBP—tributyl phosphate Na Gluconate/G.A.—sodium gluconate gluconic acidblend

In Table 8, samples S-77 to S79 show the 28 day compressive strengthresponse and increasing amount of retardation relative to the reference(S-76) as the amounts of polycarboxylate, set retarder, SIA combinationincreased from low to high in the mixtures. For the mid (S-80) and lowlevels (S-81) of the example combination (polycarboxylate, set retarder,SIA), the 15 fl.oz./cwt dosage of accelerator reduced the initial settime (amount of retardation), as compared to the initial set time ofS-76, from 3 hours to 1 hour for the mid level (S-78 vs. S-80) and from1.5 hours to slightly accelerated for the low level of the examplecombination (S-79 vs. S-81). In both cases (S-80 and S-81), 28-daycompressive strengths increased with the addition of accelerator. Forthe mid (S-83) and high (S-82) levels of the example combination, thefl.oz./cwt dosage of accelerator reduced the initial set time (amount ofretardation) as compared to S-76 from about 4 hours (S-77) to one-halfhour (S-82) for the high level and from 3 hours (S-78) to slightlyaccelerated (S-83) for the mid level of the example combination. In boththe high (S-77 and S-82) and the mid level (S-78 and S-83) samples,28-day compressive strengths were equivalent showing that the goodcompressive strength performance observed for the three componentcombination are not a result of increased setting time.

In another example of a strength improvement additive that has beenfound to be useful in the present invention are poly(hydroxyalkyl)aminessuch as triisopropanolamine. Table 9 shows the comparison of twodifferent strength improvement additives, atetrahydroxyethylethylenediamine and triisopropanolamine in combinationwith a polycarboxylate dispersant and set retarder. For all of theconcrete mixtures in the table, the polycarboxylate dispersant level washeld constant at 0.11% by cement weight, and tributyl phosphate wasadded at 0.01% so that air contents would be less than 3%.

TABLE 9 Sample S-84 S-85 S-86 S-87 S-88 S-89 Cement (lbs/yd3) 511 510511 512 511 511 Sand (lbs/yd3) 1321 1347 1348 1351 1350 1330 Stone(lbs/yd3) 1864 1901 1903 1907 1905 1877 Water (lbs/yd3) 333 290 290 291291 309 Water/Cement 0.65 0.57 0.57 0.57 0.57 0.60 Sand/Aggregate 0.430.43 0.43 0.43 0.43 0.43 PC Disp (% cwt) 0.11 0.11 0.11 0.11 0.11 NaGluconate/G.A. 0.03 0.03 0.03 (%/cwt) Tetrahydroxyethyl 0.03 0.03ethylenediamine (% cwt) Triisopropanolamine 0.03 (% cwt) TBP (% cwt)0.01 0.01 0.01 0.01 0.01 Slump (in) 8.00 8.00 8.00 8.50 6.75 8.00 % Air1.0 2.2 2.1 1.9 2.0 2.0 Initial Set (Hrs.) 5.58 6.62 6.85 6.75 6.05 5.93Compressive Strengths (psi)  7 Day 3260 4440 4710 4950 4730 4450 28 Day5060 6200 6760 7080 6600 5960 PC Disp—polycarboxylate dispersant NaGluconate/G.A.—sodium gluconate gluconic acid blend TBP—tributylphosphate

Table 9 shows the setting time and 28-day compressive strengthcomparisons of polycarboxylate dispersant only (S-89), polycarboxylatedispersant plus set retarder (S-85), and polycarboxylate dispersant plusset retarder and tetrahydroxyethylethylenediamine (S-86) andpolycarboxylate dispersant plus set retarder and poly(hydroxyalkyl)amine(S-87). Relative to the polycarboxylate only reference (S-89), additionof set retarder (S-85) increased setting time by about 40 minutes andincreased 28-day compressive strength. Sample S-86, containing thetetrahydroxyethylethylenediamine, and S-87, containingpoly(hydroxyalkyl)amine, show a similar increase in 28-day compressivestrength over the polycarboxylate plus set retarder without asignificant change in setting time.

An unexpected performance improvement of the three component combinationof polycarboxylate dispersant, retarder and strength improvementadditive is the significant increase in very early compressive strengthin the cementitious compositions. Tables 10 and 11 show 12-hourcompressive strength comparisons between a polycarboxylate dispersantand the combination of polycarboxylate dispersant, retarder and strengthimprovement additive. The mix design was based on a nominal cementcontent of 700 lb/yd³ using a Type I cement (Table 10) and a Type IIIcement (Table 11). For all of the concrete mixtures in Table 10, thepolycarboxylate dispersant level was held constant at 0.11% to 0.12% bycement weight, and an EO/PO type defoamer was used at 0.0029% by cementweight. For all of the concrete mixtures in Table 11, thepolycarboxylate dispersant level was held constant at 0.20 to 0.22% bycement weight, and an EO/PO type defoamer was used at a levelproportional to the polycarboxylate dispersant as in Table 10.

TABLE 10 Sample S-90 S-91 S-92 S-93 Cement (lbs/yd3) 702 699 698 702Sand (lbs/yd3) 1268 1263 1261 1268 Stone (lbs/yd3) 1818 1810 1807 1818Water (lbs/yd3) 286 285 284 286 Water/Cement 0.407 0.407 0.407 0.407Sand/Aggregate 0.43 0.43 0.43 0.43 PC Disp. (% cwt) 0.122 0.112 0.1120.122 Polysacchride (% cwt) 0.0001 0.016 Na Gluconate/G.A. (% cwt)0.0026 SIA (% cwt) 0.0001 0.016 0.0016 Defoamer 0.0029 0.0029 0.00290.0029 Slump (in) 8.00 8.50 8.50 7.75 Air Content (%) 2.2 2.6 2.8 2.2Initial Set (Hrs) 4.98 5.10 5.20 5.05 Compressive Strengths (psi) 12 hr1290 1610 1750 1690 1 Day 3670 4060 4200 3740 PC Disp - polycarboxylatedispersant SIA - strength improvement additive Na Gluconate/G.A. -sodium gluconate gluconic acid blend

Table 10 shows the setting time and 12 hour compressive strengthcomparisons of polycarboxylate dispersant only (S-90), andpolycarboxylate dispersant plus set retarder and strength improvementadditive (S-91 to S-93). Relative to the polycarboxylate only reference(S-90), mixtures containing the three component combination (S-91 toS-93) had similar setting times and significantly increased 12 hourcompressive strengths.

TABLE 11 Sample S-94 S-95 S-96 S-97 S-98 Cement (lbs/yd3) 706 703 703703 705 Sand (lbs/yd3) 1281 1276 1276 1275 1280 Stone (lbs/yd3) 18371830 1830 1828 1836 Water (lbs/yd3) 283 282 282 281 282 Water/Cement0.400 0.400 0.400 0.400 0.400 Sand/Aggregate 0.43 0.43 0.43 0.43 0.43 PCDisp. (% cwt) 0.204 0.213 0.214 0.214 0.225 Polysacchride (% cwt) 0.01950.0076 0.029 Na Gluconate/G.A. (% cwt) 0.0044 SIA (% cwt) 0.0265 0.00760.029 0.0027 Defoamer 0.0048 0.0049 0.0054 0.0054 0.005 Slump (in) 8.759.00 8.00 8.50 8.00 Air Content (%) 1.6 2.0 2.0 2.1 1.7 Initial Set(Hrs.) 3.03 4.08 3.61 4.05 3.43 Compressive Strengths (psi) 12 Hour 39304260 4580 4380 4300 1 Day 5690 6480 6420 6530 6260 PC Disp -polycarboxylate dispersant SIA - strength improvement additive NaGluconate/G.A. - sodium gluconate gluconic acid blend

In Table 11, mixture samples S-95 to S-98, containing the threecomponent combination showed a slight increase in setting time relativeto the polycarboxylate only reference, and significantly increased 12hour and 1-day compressive strengths.

It will be understood that the embodiment(s) described herein is/aremerely exemplary, and that one skilled in the art may make variationsand modifications without departing from the spirit and scope of theinvention. All such variations and modifications are intended to beincluded within the scope of the invention as described hereinabove.Further, all embodiments disclosed are not necessarily in thealternative, as various embodiments of the invention may be combined toprovide the desired result.

1. A method of making a cementitious composition comprising forming amixture of water, hydraulic cement and a strength improvement admixturecomposition, said admixture composition comprising the components of: a.polycarboxylate dispersant; b. set retarder; and c. a strengthimprovement additive selected from the group consisting ofpoly(hydroxyalkylated)polyethyleneamines,poly(hydroxyalkylated)polyethylenepolyamines,poly(hydroxyalkylated)polyethyleneimines,poly(hydroxyalkylated)polyamines, hydrazines, 1,2-diaminopropane,polyglycoldiamine, poly(hydroxyalkyl)amines and mixtures thereof;wherein the amount of polycarboxylate dispersant is from about 5% toabout 80%, the set retarder is from about 0.5% to about 40%, and thestrength improvement additive is from about 0.5% to about 40% based onthe total dry weight of the polycarboxylate dispersant, the set retarderand the strength improvement additive.
 2. The method of claim 1, whereinthe amount of polycarboxylate dispersant is from about 0.02% to about2%, the set retarder is from about 0.002% to about 0.2%, the strengthimprovement additive is from about 0.0001% to about 0.2% by weight ofcementitious binder.
 3. The method of claim 1, wherein the amount ofpolycarboxylate dispersant is from about 0.02% to about 0.24%, the setretarder is from about 0.005% to about 0.08%, the strength improvementadditive is from about 0.004% to about 0.08% by weight of cementitiousbinder.
 4. The method of claim 1, wherein the strength improvementadditive is selected from the group consisting ofdi(hydroxyethyl)1,2-diaminopropane,tetra(hydroxyethyl)1,2-diaminopropane, di(hydroxyethyl)hydrazine,tetra(hydroxyethyl)hydrazine, ethoxylated polyglycoldiamine,triisopropanolamine and mixtures thereof.
 5. The method of claim 1,wherein the strength improvement additive is selected from the groupconsisting of N,N,N′-tri-(hydroxyethyl)ethylenediamine,N,N,N′-tri-(hydroxyethyl)diethylenediamine,N,N′-di-(hydroxyethyl)ethylenediamine,N,N′-bis(2-hydroxypropyl)diethylenetriamine,N,N,N′,N′-tetra(hydroxyethyl)ethylenediamine,N,N,N′,N′,N″-penta(hydroxyethyl)diethylenetriamine,N,N′-bis(2-hydroxypropyl)-N,N,N′-tri(hydroxyethyl)diethylenetriamine,and mixtures thereof.
 6. The method of claim 1, wherein the strengthimprovement additive comprises poly(hydroxyethyl)polyethyleneimine. 7.The method of claim 1, wherein the strength improvement additivecomprises poly(hydroxyalkylated)polyethyleneamine having the followingformula:

wherein x is 1, 2 or 3 and R is selected from the group consisting ofhydrogen, 2-hydroxyethyl, and 2-hydroxypropyl, each R can be the same ordifferent, and at least 40% of the R groups are hydroxyalkyl, with nomore than 40% of the R groups being hydroxypropyl.
 8. The method ofclaim 1, wherein the strength improvement additive has the followingformula:(R′)₂NCH₂CH₂N(R′)₂ wherein R′ is (CH₂CH₂O)_(y)H, wherein y is 0, 1 or 2,wherein no more than one-half (½) of the compounds of the formula have yequal to 0, and each R′ can be the same or different.
 9. The method ofclaim 1, wherein the strength improvement additive has the followingformula:

wherein R″ is selected from the group consisting of (CH₂CH₂O)_(y)H and

wherein X is a covalent bond or a divalent organic radical selected fromthe group consisting of CH₂, CH₂CH₂,

and CH₂CH₂CH₂OCH₂CH₂OCH₂CH₂OCH₂CH₂CH₂; wherein y and v are 0, 1 or 2;wherein w is 0 or 1; wherein v and w cannot both be 0; and wherein nomore than one-half (½) of the R″ groups are hydrogen.
 10. The method ofclaim 1, wherein the strength improvement additive comprises EthoxylatedAmine HH, having a typical analysis of:

aminoethyl piperazine: 50% to 70% by weight triethylene tetramine: 40%maximum by weight others: balance.
 11. The method of claim 1, whereinthe strength improvement additive has the following formula:(R³)_(n)H_(q)N Wherein R³ is [(CHR⁴)_(m)(CHR⁴)O]_(p)H; wherein R⁴ isindependently H or CH₃; wherein m=1 or 2; wherein n=2 or 3; wherein p=1or 2; wherein q=3-n; and each R³ can be the same or different.
 12. Themethod of claim 1 wherein the set retarder is selected from the groupconsisting of an oxy-boron compound, a polyphosphonic acid, a carboxylicacid, a hydroxycarboxylic acid, polycarboxylic acid, hydroxylatedcarboxylic acid, fumaric, itaconic, malonic, borax, gluconic, andtartaric acid, lignosulfonates, ascorbic acid, isoascorbic acid,sulphonic acid-acrylic acid copolymer, and their corresponding salts,polyhydroxysilane, polyacrylamide, carbohydrates and mixtures thereof.13. The method of claim 1, wherein the cement is selected from the groupconsisting of portland cement, modified portland cement, or masonrycement, and mixtures thereof.
 14. The method of claim 1 wherein thehydraulic cement is portland cement.
 15. The method of claim 1 furthercomprising a cement admixture or additive that is selected from thegroup consisting of set accelerator, air detraining agent, airentraining agent, foaming agent, corrosion inhibitor, shrinkage reducingadmixture, water reducer, fiber, pigment, pozzolan, clay, strengthenhancing agents, rheology modifying agents, water repellents, wettingagents, water soluble polymers, dampproofing admixtures, gas formers,permeability reducers, pumping aids, fungicidal admixtures, germicidaladmixtures, insecticidal admixtures, aggregates, alkali-reactionreducers, bonding admixtures, and mixtures thereof.
 16. The method ofclaim 15, wherein the aggregate is at least one of silica, quartz,crushed round marble, glass spheres, granite, limestone, calcite,feldspar, alluvial sands, and sand.
 17. The method of claim 15, whereinthe pozzolan is at least one of natural pozzolan, metakaolin, fly ash,silica fume, calcined clay, and blast furnace slag.
 18. The method ofclaim 1 wherein the polycarboxylate dispersant comprises at least oneof: a) a dispersant of Formula (I):

wherein in Formula (I) X is at least one of hydrogen, an alkali earthmetal ion, an alkaline earth metal ion, ammonium ion, or amine; R is atleast one of C₁ to C₆ alkyl(ene) ether or mixtures thereof or C₁ to C₆alkyl(ene)imine or mixtures thereof; Q is at least one of oxygen, NH, orsulfur; p is a number from 1 to about 300 resulting in at least one of alinear side chain or branched side chain; R₁ is at least one ofhydrogen, C₁ to C₂₀ hydrocarbon, or functionalized hydrocarboncontaining at least one of —OH, —COOH, an ester or amide derivative of—COOH, sulfonic acid, an ester or amide derivative of sulfonic acid,amine, or epoxy; Y is at least one of hydrogen, an alkali earth metalion, an alkaline earth metal ion, ammonium ion, amine, a hydrophobichydrocarbon or polyalkylene oxide moiety that functions as a defoamer;m, m′, m″, n, n′, and n″ are each independently 0 or an integer between1 and about 20; Z is a moiety containing at least one of i) at least oneamine and one acid group, ii) two functional groups capable ofincorporating into the backbone selected from the group consisting ofdianhydrides, dialdehydes, and di-acid-chlorides, or iii) an imideresidue; and wherein a, b, c, and d reflect the mole fraction of eachunit wherein the sum of a, b, c, and d equal one, wherein a, b, c, and dare each a value greater than or equal to zero and less than one, and atleast two of a, b, c, and d are greater than zero; b) a dispersant ofFormula (II):

wherein in Formula (II): A is COOM or optionally in the “y” structure anacid anhydride group (—CO—O—CO—) is formed in place of the A groupsbetween the carbon atoms to which the A groups are bonded to form ananhydride; B is COOM M is hydrogen, a transition metal cation, theresidue of a hydrophobic polyalkylene glycol or polysiloxane, an alkalimetal ion, an alkaline earth metal ion, ferrous ion, aluminum ion,(alkanol)ammonium ion, or (alkyl)ammonium ion; R is a C₂₋₆ alkyleneradical; R1 is a C₁₋₂₀ alkyl, C₆₋₉ cycloalkyl, or phenyl group; x, y,and z are a number from 0.01 to 100; m is a number from 1 to 100; and nis a number from 10 to 100; c) a dispersant comprising at least onepolymer or a salt thereof having the form of a copolymer of i) a maleicanhydride half-ester with a compound of the formula RO(AO)_(m)H, whereinR is a C₁-C₂₀ alkyl group, A is a C₂₋₄ alkylene group, and m is aninteger from 2-16; and ii) a monomer having the formulaCH₂═CHCH₂—(OA)_(n)OR, wherein n is an integer from 1-90 and R is a C₁₋₂₀alkyl group; d) a dispersant obtained by copolymerizing 5 to 98% byweight of an (alkoxy)polyalkylene glycol mono(meth)acrylic ester monomer(a) represented by the following general formula (1):

wherein R₁ stands for hydrogen atom or a methyl group, R₂O for onespecies or a mixture of two or more species of oxyalkylene group of 2 to4 carbon atoms, providing two or more species of the mixture may beadded either in the form of a block or in a random form, R₃ for ahydrogen atom or an alkyl group of 1 to 5 carbon atoms, and m is a valueindicating the average addition mol number of oxyalkylene groups that isan integer in the range of 1 to 100, 95 to 2% by weight of a(meth)acrylic acid monomer (b) represented by the above general formula(2), wherein R₄ and R₅ are each independently a hydrogen atom or amethyl group, and M₁ for a hydrogen atom, a monovalent metal atom, adivalent metal atom, an ammonium group, or an organic amine group, and 0to 50% by weight of other monomer (c) copolymerizable with thesemonomers, provided that the total amount of (a), (b), and (c) is 100% byweight; e) a graft polymer that is a polycarboxylic acid or a saltthereof, having side chains derived from at least one species selectedfrom the group consisting of oligoalkyleneglycols, polyalcohols,polyoxyalkylene amines, and polyalkylene glycols; f) a dispersant ofFormula (III):

wherein in Formula (III): D=a component selected from the groupconsisting of the structure d1, the structure d2, and mixtures thereof;X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-Methyl Phenyl, or Sulfonated Phenyl;Y=H or —COOM; R=H or CH₃; Z=H, —SO₃M, —PO₃M, —COOM, —O(CH₂)_(n)OR₃ wheren=2 to 6, —COOR₃, or —(CH₂)_(n)OR₃ where n=0 to 6, —CONHR₃,—CONHC(CH₃)₂CH₂SO₃M, —COO(CHR₄)_(n)OH where n=2 to 6, or —O(CH₂)_(n)OR₄wherein n=2 to 6; R₁, R₂, R₃, R₅ are each independently —(CHRCH₂O)_(m)R₄random copolymer of oxyethylene units and oxypropylene units where m=10to 500 and wherein the amount of oxyethylene in the random copolymer isfrom about 60% to 100% and the amount of oxypropylene in the randomcopolymer is from 0% to about 40%; R₄=H, Methyl, C₂ to about C₆ Alkyl,or about C₆ to about C₁₀ aryl; M=H, Alkali Metal, Alkaline Earth Metal,Ammonium, Amine, triethanol amine, Methyl, or C₂ to about C₆ Alkyl; a=0to about 0.8; b=about 0.2 to about 1.0; c=0 to about 0.5; d=0 to about0.5; and wherein a, b, c, and d represent the mole fraction of each unitand the sum of a, b, c, and d is 1.0; g) a dispersant of Formula (IV):

wherein in Formula (IV): the “b” structure is one of a carboxylic acidmonomer, an ethylenically unsaturated monomer, or maleic anhydridewherein an acid anhydride group (—CO—O—CO—) is formed in place of thegroups Y and Z between the carbon atoms to which the groups Y and Z arebonded respectively, and the “b” structure must include at least onemoiety with a pendant ester linkage and at least one moiety with apendant amide linkage; X=H, CH₃, C₂ to C₆ Alkyl, Phenyl, p-MethylPhenyl, p-Ethyl Phenyl, Carboxylated Phenyl, or Sulfonated Phenyl; Y=H,—COOM, —COOH, or W; W=a hydrophobic defoamer represented by the formulaR₅O—(CH₂CH₂O)_(s)—(CH₂C(CH₃)HO)_(t)—(CH₂CH₂O)_(u) where s, t, and u areintegers from 0 to 200 with the proviso that t>(s+u) and wherein thetotal amount of hydrophobic defoamer is present in an amount less thanabout 10% by weight of the polycarboxylate dispersant; Z=H, —COOM,—O(CH₂)_(n)OR₃ where n=2 to 6, —COOR₃, —(CH₂)_(n)OR₃ where n=0 to 6, or—CONHR₃; R₁=H, or CH₃; R₂, R₃, are each independently a random copolymerof oxyethylene units and oxypropylene units of the general formula—(CH(R₁)CH₂O)_(m)R₄ where m=10 to 500 and wherein the amount ofoxyethylene in the random copolymer is from about 60% to 100% and theamount of oxypropylene in the random copolymer is from 0% to about 40%;R₄=H, Methyl, or C₂ to C₈ Alkyl; R₅=C₁ to C₁₈ alkyl or C₆ to C₁₈ alkylaryl; M=Alkali Metal, Alkaline Earth Metal, Ammonia, Amine, monoethanolamine, diethanol amine, triethanol amine, morpholine, imidazole;a=0.01-0.8; b=0.2-0.99; c=0-0.5; and wherein a, b, c represent the molefraction of each unit and the sum of a, b, and c, is 1; h) a randomcopolymer corresponding to the following Formula (V) in free acid orsalt form having the following monomer units and numbers of monomerunits:

wherein A is selected from the moieties (i) or (ii) (i) —CR₁R₂—CR₃R₄(ii)

wherein R₁ and R₃ are selected from substituted benzene, C₁₋₈ alkyl,C₂₋₈ alkenyl, C₂₋₈ alkylcarbonyl, C₁₋₈ alkoxy, carboxyl, hydrogen, and aring, R₂ and R₄ are selected from the group consisting of hydrogen andC₁₋₄ alkyl, wherein R₁ and R₃ can together with R₂ and/or R₄ when R₂and/or R₄ are C₁₋₄ alkyl form the ring; R₇, R₈, R₉, and R₁₀ areindividually selected from the group consisting of hydrogen, C₁₋₆ alkyl,and a C₂₋₈ hydrocarbon chain, wherein R₁ and R₃ together with R₇ and/orR₈, R₉, and R₁₀ form the C₂₋₈ hydrocarbon chain joining the carbon atomsto which they are attached, the hydrocarbon chain optionally having atleast one anionic group, wherein the at least one anionic group isoptionally sulfonic; M is selected from the group consisting ofhydrogen, and the residue of a hydrophobic polyalkylene glycol or apolysiloxane, with the proviso that when A is (ii) and M is the residueof a hydrophobic polyalkylene glycol, M must be different from the group—(R₅O)_(m)R₆; R₅ is a C₂₋₈ alkylene radical; R₆ is selected from thegroup consisting of C₁₋₂₀ alkyl, C₆₋₉ cycloalkyl and phenyl; n, x, and zare numbers from 1 to 100; y is 0 to 100; m is 2 to 1000; the ratio of xto (y+z) is from 1:10 to 10:1 and the ratio of y:z is from 5:1 to 1:100;i) a copolymer of oxyalkyleneglycol-alkenyl ethers and unsaturateddicarboxylic acids, comprising: i) 0 to 90 mol % of at least onecomponent of the formula 3a or 3b:

or

wherein M is a hydrogen atom, a mono- or divalent metal cation, anammonium ion or an organic amine residue, a is 1, or when M is adivalent metal cation a is ½; wherein X is —OM_(a),—O—(C_(m)H_(2m)O)_(n)—R¹ in which R¹ is a hydrogen atom, an aliphatichydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulphonic substitutedaryl radical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to100, —NHR₂, —N(R²)₂ or mixtures thereof in which R²=R¹ or —CO—NH₂; andwherein Y is an oxygen atom or —NR²; ii) 1 to 89 mol % of components ofthe general formula 4:

wherein R₃ is a hydrogen atom or an aliphatic hydrocarbon radicalcontaining from 1 to 5 carbon atoms, p is 0 to 3, and R₁ is hydrogen, analiphatic hydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulfonic substituted arylradical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to 100,and iii) 0.1 to 10 mol % of at least one component of the formula 5a or5b:

or

wherein S is a hydrogen atom or —COOM_(a) or —COOR₅, T is —COOR₅, —W—R₇,—CO—[—NH—(CH2)3)-]_(s)-W—R₇, —CO—O—(CH₂)_(z)—W—R₇, a radical of thegeneral formula:

or —(CH₂)_(z)—V—(CH₂)_(z)—CH═CH—R₁, or when S is —COOR₅ or —COOM_(a), U₁is —CO—NHM—, —O— or —CH₂O, U₂ is —NH—CO—, —O— or —OCH₂, V is—O—CO—C₆H₄—CO—O— or —W—, and W is

R4 is a hydrogen atom or a methyl radical, R5 is an aliphatichydrocarbon radical containing 3 to 20 carbon atoms, a cycloaliphatichydrocarbon radical containing 5 to 8 carbon atoms or an aryl radicalcontaining 6 to 14 carbon atoms, R₆=R₁ or

or

R₇=R₁ or

or

r is 2 to 100, s is 1 or 2, x is 1 to 150, y is 0 to 15 and z is 0 to 4;iv) 0 to 90 mol % of at least one component of the formula 6a, 6b, or6c:

wherein M is a hydrogen atom, a mono- or divalent metal cation, anammonium ion or an organic amine residue, a is 1, or when M is adivalent metal cation a is ½; wherein X is —OM_(a),—O—(C_(m)H_(2m)O)_(n)—R¹ in which R¹ is a hydrogen atom, an aliphatichydrocarbon radical containing from 1 to 20 carbon atoms, acycloaliphatic hydrocarbon radical containing 5 to 8 carbon atoms or anoptionally hydroxyl, carboxyl, C₁₋₁₄ alkyl, or sulphonic substitutedaryl radical containing 6 to 14 carbon atoms, m is 2 to 4, and n is 0 to100, —NH—(C_(m)H_(2m)O)_(n)—R¹, —NHR₂, —N(R²)₂ or mixtures thereof inwhich R²=R¹ or —CO—NH₂; and wherein Y is an oxygen atom or —NR²; j) acopolymer of dicarboxylic acid derivatives and oxyalkyleneglycol-alkenyl ethers, comprising: i) 1 to 90 mol. % of at least onemember selected from the group consisting of structural units of formula7a and formula 7b:

wherein M is H, a monovalent metal cation, a divalent metal cation, anammonium ion or an organic amine; a is ½ when M is a divalent metalcation or 1 when M is a monovalent metal cation; wherein R¹ is —OM_(a),or —O—(C_(m)H_(2m)O)_(n)—R² wherein R² is H, a C₁₋₂₀ aliphatichydrocarbon, a C₅₋₈ cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that isoptionally substituted with at least one member selected from the groupconsisting of —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2); m is 2 to 4; nis 1 to 200; ii) 0.5 to 80 mol. % of the structural units of formula 8:

wherein R³ is H or a C₁₋₅ aliphatic hydrocarbon; p is 0 to 3; R² is H, aC₁₋₂₀ aliphatic hydrocarbon, a C₅₋₈ cycloaliphatic hydrocarbon, or aC₆₋₁₄ aryl that is optionally substituted with at least one memberselected from the group consisting of —COOM_(a), —(SO₃)M_(a), and—(PO₃)M_(a2); m is 2 to 4; n is 1 to 200; iii) 0.5 to 80 mol. %structural units selected from the group consisting of formula 9a andformula 9b:

wherein R⁴ is H, C₁₋₂₀ aliphatic hydrocarbon that is optionallysubstituted with at least one hydroxyl group, —(C_(m)H_(2m)O)_(n)—R²,—CO—NH—R², C₅₋₈ cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that isoptionally substituted with at least one member selected from the groupconsisting of —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2); M is H, amonovalent metal cation, a divalent metal cation, an ammonium ion or anorganic amine; a is ½ when M is a divalent metal cation or 1 when M is amonovalent metal cation; R² is H, a C₁₋₂₀ aliphatic hydrocarbon, a C₅₋₈cycloaliphatic hydrocarbon, or a C₆₋₁₄ aryl that is optionallysubstituted with at least one member selected from the group consistingof —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2); m is 2 to 4; n is 1 to 200;iv) 1 to 90 mol. % of structural units of formula 10

wherein R⁵ is methyl, or methylene group, wherein R⁵ forms one or more 5to 8 membered rings with R⁷; R⁶ is H, methyl, or ethyl; R⁷ is H, a C₁₋₂₀aliphatic hydrocarbon, a C₆₋₁₄ aryl that is optionally substituted withat least one member selected from the group consisting of —COOM_(a),—(SO₃)M_(a), and —(PO₃)M_(a2), a C₅₋₈ cycloaliphatic hydrocarbon,—OCOR⁴, —OR⁴, and —COOR⁴, wherein R⁴ is H, a C₁₋₂₀ aliphatic hydrocarbonthat is optionally substituted with at least one —OH,—(C_(m)H_(2m)O)_(n)—R², —CO—NH—R², C₅₋₈ cycloaliphatic hydrocarbon, or aC₆₋₁₄ aryl residue that is optionally substituted with a member selectedfrom the group consisting of —COOM_(a), —(SO₃)M_(a), and —(PO₃)M_(a2).